Perhalocarbon compounds and method of preparing them



Patented Mar. 9, 1954 i i-KGB PERHALOCARBON COMPOUNDS AND METHGD OFPREPARING THEM William T. Miller, Ithaca, N. Y.

No Drawing. Application August 30, 1950,

, Serial No. 182,423

22 Claims. 1

This invention relates to perhalocarbon compounds and the method ofpreparing them. In one aspect, the invention relates to the productionof functional derivatives of unsaturated perhalocarbons. In another moreparticular aspect, the invention relates to the production ofperhaloallyl functional derivatives of unsaturated perfluorocarbons byintermolecular replacements of allylic halogens. This invention is acontinuation-in-part of my prior and co-pending application Serial No.601,387, filed June 25, 1945, now abandoned.

It has been found that perhalocarbon compounds and their derivatives areof value in various industrial applications such as protective coatingcompositions, electrical insulation, dielectrics, lubrication,refrigeration and the like. Typical of these perhalocarbons are theperfluorocarbons and chloro-derivatives of perfiuorocarbon compounds,which may be prepared by the dimerization and addition reactions offluorine with monoand di-olefins, by methods such as thermal reactionsof perhaloolefins or by other methods. The principal type productsobtained from reaction between fluorine and perhaloethylenes are thesimple or normal addition product and the dimer addition product. Thedimerization reaction is important in that it leads to the formation ofhigher molecular weight compounds from low molecular weight olefins. Anexample of such reaction, is the fluorination ofdifluorodichloroethylene at a temperature between about 70 C. and about'75 C. to give a 40% yield of the dimer addition products (C4C14Fe orCFzClCFClCFClCFzCl) 1,2,3,4 tetrachl'oroperfluorobutane. By-productsfrom this fluorination reaction of are mainly butanes containing up to 6chlorine atoms and ethanes containing from 1 to 4 chlorine atoms. Nearlyquantitative conversion of the dimer C4C14Fs into perfluorobutadiene-L3has been accomplished by dechlorination with zinc dust under improvedconditions for isolation and recovery of the product. Perfluorobutadieneand the perfluorochlorobutadienes prepared in this way may be convertedinto a variety of perfiuoro products by fluorination and polymerizationprocedures. Dechlorination of the dimer addition product of CFC1=CFC1.(CFaCICFClCFClCFzC'l) with zinc dust and dioxane solution may becarried out so as to give substantial yields of1,4-dichloroperfluorobutene- 2 (CF2C1CF=CFCF2C1) along withperfluorobutadiene -1,3.

2 Using a Pyrex reactor tube 1" in diameter heated over a 1' section toa maximum temperature of 550-560 0., trifluorochloroethylene passingthrough this reactor at the rate of 30-40 grams per hour reacts to givethe following approximate amounts of principal products:

0 F (Hg-C F=C F2 1 -2 7 CF201-CF=OF2 5-10% 0 CF2C]CFC1CF=OF2 35%}CF2-CFCIOFC1OF2 30% 0 High boiling residues 5% In other experiments theratio of propenes obtained was approximately one to one.

For example, CF2=CFC1 passed at a 45 g./hr. rate through each of six 3 x30 cm. Pyrex glass reactor tubes of a small scale pilot plant reactedwhen heated to 550-560 C. for 15 seconds to give the followingapproximate yields of major products:

Lower B. P. by-products 11% These average results were obtained from atotal pass of about 20 kilograms of CF2=CFCl in three units with anaverage conversion of about At higher temperatures the proportion ofpropenes in the reaction product is increased.

It will be noted that among the olefinic compounds prepared by the abovemethods, are those which contain allylic halogen, that is, a halogenatom which is bonded to a carbon atom adjacent to a doubly bonded carbonatom, as exemplified by the compound CF2=CFCF2C1 in which the chlorineatom is referred to as the allylic chlorine, and is mere reactive thanthe fluorine atoms attached to the same carbon atom. In perfluorounsaturated compounds, allylic fluorine atoms are also more reactivethan the fluorine atoms in the corresponding saturated compound.

It is, therefore, an object of the present invention to producefunctional derivatives of unsaturated perhalo compounds.

Another object of the invention is to produce functional derivatives ofunsaturated perhalo compounds by a method of intermolecular replacement.

Other objects and advantages of the invention will become apparent fromthe following more detailed disclosure.

It has now been found, as more fully hereinafter described, that it ispossible to bring about selective reaction between the allylic halogenand reagents comprising inorganic metal compounds, to produce a newclass of compounds comprising perhaloallyl functional derivatives byintermolecular replacement of the allylic halogen with an ion ofinorganic metal compounds, in which the compounds produced are ofprimary importance in providing valuable new intermediates for polymercoatings, plastic compositions and the like, or as insecticides andother new chemical compositions. The functional derivatives ofunsaturated perhalocarbons produced by the method of this invention areparticularly useful as synthetic intermediates for the production ofother perhalocarbon derivatives ofrelatively low molecular weight and asmonomers for polymerization to form materials of relatively highmolecular weight which are useful as lubricants, coating compositionsand the like.

A general basis for the preparation of many derivatives of fluorocarbonsresults from this discovery that primary allylic chlorine inperfluoroolefins is highly reactive with a variety of reagents. Forexample, the chlorine in such compounds as CF2=CFCF2C1(3-chloroperfluoropropene-l) reacts in a highly preferential manner ascompared with the fluorine atoms attached to the same carbon atom.

According to this invention, in its broad aspect, unsaturatedperhalocarbons having at least 3 carbon a m p m c le nd. n allylihalogen atom, are subiected to allylic replacements by reaction withinorganic. metal compounds,

which; are normally metal salts such as oyanides, thiocyanates,sulfides, iodides, nitrates, nitrites, metal alcoholates, metalphenolates, metal salts of mercaptans, and thiophenols to replace themore reactive allylic halogen with the negative ion of the inorganicmetal compound and, to produce the desired perhaloallyl functionalderivative of the unsaturated perhalocarbon. The replacement reaction ispreferably made to take place with chlorine being present as the allylichalogen in perfluorochloroolefins, as exemplified by chlorinein the3-positionin CF2=CFCF2C1 (3-chloroperfiuoropropene-l) or in(2,3edichloroperfiuoropropene-l), because of the lower cost of chlorinecompounds as compared to the bromides and iodides although the allylichalogen may also be either bromine or iodine. Thus bromine or iodi e mayappear as allylic halogen in such compounds. as CFZZCFCFZBI(3-bromoperfiuoropropene-I) and CFz=GECF2I (3-iodoperfluoropropene- 1),respectively. The replacement reaction may also be made to. take placewith secondary allylic halogens being pres- 'ent in perfluoroolefins, asillustrated by chlorine in the 3-position in3,4-dichloroperfluorobutene-1 2= CF 2C although such secondary allylicgroupin may e. somewhat less. reactive than the primary allylicgroupings indicated above.

In carryi g out the replacement reaction between the unsaturatedperhalocarbon and the inorganic metal compound, the reactants may beemployed. over a. wide range ofconcentrations depending upon theparticular reaction being carried out. In general, with neutral, saltsSuch a s d um o d it: is preferable to. utilizea considerable excess ofthe salt in orderto. obtain a faster and more complete reaction.However,

' frequently preferred as solvents.

with bases or substances which give basic reactions in solution, it isfrequently preferable to utilize an excess of the perhaloallyl halide orequivalent quantities and to add the metal compound to the allyl halideat a rate comparable to or less than the rate of reaction so as tomaintain the halide in excess and avoid the presence at any time, ofappreciable concentrations of the base. This is especially importantwhen alcohols are utilized as solvents because of the base catalyzedaddition of alcohols to perhaloolefins which may occur. Primary alcoholsundergo addition most readily so that secondary or tertiary alcohols asisopropyl and tertiary butyl alcohol are Other solvents such as acetone,methyl ethyl ketone, diethyl ketone, dioxane and other ketones andethers may also be utilized. Ihe salt product of the reaction should beas sparingly soluble as possible. Where the reactant salt solution isadded to the olefin gradually, this may be done by continuous extractionof the reactant salt with a relatively poor solvent. While the solventemployed is one which is preferably in a nonaqueous condition, it isnevertheless preferred that this solvent be soluble in water and wateror aqueous solvents may beused to advantage in certain cases such aswhen no non-aqueous solvent can be found to. dissolve the reactant salt.In general, the proper quantity ofsolvent employed will be that amountwhich is necessary to dissolve the required molweight of the inorganicmetal compound in the solvent. However, satisfactory reactions may becarried out utilizing sparingly soluble salts with an excess of the saltpresent so as to maintain at all times a saturated solution, even thougha molar quantity of the salt will not dissolve initially. The saltformed by the reaction should be less soluble than the reactant salt.The ratio of solubilities should be as great as possible. For thisreason allyl chlorides are frequently preferred to iodides and bromides.

The reaction between the unsaturated perhalocarbon, containing theallylic halogen, and the inorganic metal compound carried out in asuitable mixing vessel with sufficient stirring to. insure thoroughmixing, so that the allylic halogen to be replaced will be obtainedinthe form of a. fine powdered precipitated salt of the inorganic metalcompound. The reaction iscarried. outv at atmospheric pressure and at atem perature between about #10." C. and about 200 C., with a temperaturebetween about 5 C. and about 100- C; being preferred. Complete admixtureand reaction between the inorganic metal compound and the unsaturatedperhalocarbon starting material is indicated either by examination ofthe boiling point at reflux, or by the quantity: of precipitated salt,or by failure of additional salt to precipitate or by other methods fordetermining the composition of the reaction mixture.

Following the aforementioned complete admixture and reaction, there isobtained a mixture comprising the desired product, namely, thefunctional derivative of the unsaturated perhalocarbon in the solventand: containing an excess of the inorganic metal compound, as: forexample'i'n the case of neutral salts where so-used, and also theaforementioned precipitate comprising the metallic allylic. halogensalt. This mixture is, in. general, next filtered to separate the solidmetallic. allylic. halogen salt from the filtrate comprising the desiredperhaloallyl functional derivative product in solvent and excessinorganic metal salt. This filtrate may also contain some unreactedunsaturated perhalocarbon starting material. The isolation of theproducts may also be carried out by direct distillation after separationof precipitated salt by filtration, or by direct distillation withoutfiltration, depending upon the particular products and the solvent whichare present, the boiling points and stability of the products.

The filtrate thus obtained is next water-washed at room temperature witha quantity of water sufiicient to dissolve the solvent and excessinorganic metal compound present. The resulting water-washed filtrate isthen subjected to phase separation to obtain an aqueous phase comprisingan aqueous solution of the solvent and inorganic metal compound, and anon-aqueous or organic phase comprising the desired endproduct and anyunreacted quantities of the original unsaturated perhalocarbon startingmaterial. In order to separate any quantities of the solvent that mayremain in the organic product phase thus separated, .it is desirable towash this phase several times with water, or in some instances when aketone solvent which forms an addition compound with sodium bisulfite isutilized, a fairly concentrated solution of aqueous sodium bisulfite,having a concentration of at least 20% may be employed. Such procedureis of use for certain ketones where the products do not react with thebisulflte. It is also possible, if so desired, to separate any unusedportion of the solvent that may remain in the aforementioned organicphase by direct distillation or drying.

The following examples will serve to illustrate some of the types of thefunctional derivatives of unsaturated perhalocarbons obtainable and themethod of preparing them according to the present invention.

Example I A one liter three-necked glass flask was fitted with adropping funnel, a Herschberg-type stirrer with a gas-tight shaft seal,and a short packed distilling column surmounted by a refrigerated refluxcondenser. One-tenth liter of pure anhydrous methyl alcohol was placedin the flask, cooled to ice temperature, the stirrer started and theflask swept out with dry nitrogen. 119 grams of perfluoroallyl chloride(CF2=CFCF2Cl) was then added. 11.5 grams of clean sodium metal wasdissolved in 0.230 liters of anhydrous methyl alcohol and the resultingsolution placed in the dropping funnel and slowly added to the stirredalcohol perfluoroallyl chloride mixture during a 4 period of about threehours. Heat was evolved and the flask was cooled externally so as tomaintain the contents under 9 C. At the end of the reaction the flaskcontents were found to be neutral to litmus. Distillation yielded a lowboiling fraction, boiling largely at 34 C. This fraction was treatedwith anhydrous calcium chloride and then distilled from P205, afterfiltration to remove the calcium chloride, to yield approximately 70% ofthe theoretical yield of B-methoxyperfluoropropene (CFz CFCFzOCHs). The3-methoxyperfiuoropropene had the following properties: B. P. 385 C.,uncorrected; D4 1.358; n 1.296; F. P. below Dry Ice temperature;molecular weight found 161, as compared with a calculated value of 162.3-methoxyperfluoropropene was unsaturated to potassium permanganate in 6acetone, and yielded a dibromide on brominetion in a sealed tube.

Example II A one liter three-necked glass flask was fitted with a gasinlet tube and a thermometer, which extended well into the flask, astirrer with a gas-tight shaft seal and a water-cooled reflux condenserwhich was surmounted by a Dry-Ice cooled reflux condenser. 200 grams ofpowdered sodium iodide was placed in the flask and onehalf liter of pureredistilled methyl ethyl ketone added. The stirrer was started and theflask and condensing system swept out with dry carbon dioxide gas. Acarbon dioxid blanket was maintained at the condenser outlet during thereaction period and the reaction flask was protected from strong light.161 grams of 3-chloroperfluoropropene (CFz=CFCF2Cl) was distilled intothe reaction flask through the gas inlet tube and the mixture stirredfor three hours. The flask contents were then heated to gentle reflux bymeans of an oil bath with stirring maintained for the duration of therun or about 100 hours.

4 During this period the reflux temperature rose Example III A one literthree-necked flask was fitted with a dropping funnel, a Herschberg-typestirrer with a shaft seal and an ice-cooled reflux condenser. 50 gramsof powdered sodium cyanide, 45 cc. of water and 5 cc. of pyridin wereplaced in the flask and warmed gently with stirring until the cyanidewas dissolved. The air was displaced from the flask with nitrogen andgrams of 3-chloroperfluoropropene (CF2=CFCFzCl), dissolved in cc. ofanhydrous tertiary butyl alcohol, added very slowly with stirring whilemaintaining the reaction mixture at gentle reflux by oil bath heating.After the reaction was essentially complete, as evidenced by the rate ofsodium chloride precipitation, about 100 cc. of toluene was added. Themixture was filtered to separate precipitated salt and the organic layerseparated and washed thoroughly with cold water. After drying andseparation of unreacted starting material to a B. P, of 15 C., the lowboiling nitrile fraction was collected from 35 C. to about 55 C.Redistillation yielded perfluoroallyl cyanide (CFz CFCFzCN), B. P. 43 C.to 48 C. (uncorrected), and a higher B. P.

residue. This product was unsaturated to potassium permanganate inacetone and added bromine when reacted in a sealed tub in the presenceof ultra-violet light. Dioxane was also found to be a suitable solventfor the reaction when substituted for the above-mentioned tertiary butylalcohol.

2,3-dichloroperfluoropropene1 ac'zmee 'Was' reacted similarly toCF2=CFCF2C1 to produce corresponding products.

Since many embodiments might be made or" the present invention and sincemany changes might be made in th embodiment described, is to beunderstood that the foregoing description is to be interpreted asillustrative only and not in a limiting sense.

I claim:

1. A process for the allylic replacement of an unsaturated perhalocarbonwhich comprises: reacting a perhalofiuoroallyl halide having at least 3carbon atoms per molecule and an allylic halogen atom selected from thegroup consisting of chlorine, bromine and iodine with a metal salt whichis capabl of releasing a negative ion in solution different from saidallylic halogen atom and selected from the group consisting of metalalcoholates, iodides, cyanides and nitrates in a solvent selected fromthe group consisting of water and a water-soluble compound, whereby saidallylic halogen atom is replaced with the negative ion of the metal saltto produce a reaction mass comprising a substituted perhalofluoroallylcompound containing the negative ion of said metal salt; and recoveringsaid perhalofluoroallyl compound from said reaction mass.

2. The process of claim 1 wherein said metal salt is a cyanide.

3. The process of claim 1 wherein said metal salt is a nitrate.

4. The process of claim 1 wherein said metal salt is an iodide.

5. The process of claim 1 wherein said metal salt is an alcoholate.

6. The process of claim 1 wherein said solvent is an alcohol.

7. The process of claim 1 wherein said solvent is a ketone.

8. The process of claim 1 wherein said solvent is an ether.

9. A process for the allylic replacement of an unsaturated perhalocarbonwhich comprises:

reacting a perhalofluoroallyl halide having at y least 3 carbon atomsper molecule and an allylic halogen atom selected from the groupconsisting of chlorine, bromine and iodine with a metal salt which iscapable of releasing a negative ion in solution different from saidallylic halogen atom and selected from the group consisting of metalalcoholates, iodides, cyanides and nitrates in a solvent selected fromthe group consisting of water and a water soluble compound at atemperature between about 10 C. and about 200 in solution difierent fromsaid allylic halogen atom and selected from the group consisting ofmetal alcoholates, iodides, cyanides and nitrates in a solvent selectedfrom the group consisting of water and a water-soluble compound at atemperature between about 5 C. and about 100 0., whereby said allylichalogen atom is replaced with the negative ion of the metal salt toproduce a reaction mass comprising a substituted perhalofluoroallylcompound containing the negative ion of said metal salt; and recoveringsaid perhalofiuoroallyl compound from said reaction mass.

11. A process for the allylic replacement or an unsaturatedperhalocarbon which comprises: reacting a perhalofluoroallyl halidehaving at least 3 carbon atoms per molecule and an allylic halogen atomselected from the group consisting of chlorine, bromine and iodine witha metal salt which is capable of releasing a negative ion in solutiondifferent from said allylic halogen atom and selected .from'the groupconsisting of metal alcoholates, iodides, cyanides and nitrates in awater-soluble solvent, whereby said allylic halogen atom is replacedwith the negative ion of the metal salt to produce a reaction masscomprising a substituted perhalofiuoroallyl compound containing thenegative ion of said metal salt, solvent and a metallic allylic halogensalt precipitate; recovering said precipitate from said reaction mass;water-washing the remaining mixture, comprising said substitutedperhalofluoroallyl compound and solvent, to dissolve said solvent andform an aqueous phase comprising said solvent and an organic phasecomprising said substituted perhalofluoroallyl compound; and separatingsaid phases.

12. A process for the allylic replacement of an unsaturatedperhalocarbon which comprises: reacting a perhalofluoroallyl halidehaving at least 3 carbon atoms per molecule and an allylic halogen atomselected from the group consisting of chlorine, bromine and iodine witha metal salt which is capable of releasing a negative ion in solutiondiiferent from said allylic halogen atom and selected from the groupconsisting of metal alcoholates, iodides, cyanides and nitrates in awater-soluble solvent at a temperature between about -10 C. and about200 0., whereby said allylic halogen atom is replaced with the negativeion of the metal salt to produce a reaction 'mass comprising asubstituted perhalofiuoroallyl compound containing the negative ion ofsaid metal salt, solvent, a metallic allylic halogen salt precipitateand unreacted unsaturated perhalocarbon; recovering said precipitatefrom said reaction mass; water-washing the remaining mixture, comprisingsaid substituted perhalofiuoroallyl compound and solvent to dissolvesaid solvent and form an aqueous phase comprising said solvent and anorganic phase comprising said substituted perhalofluoroallyl compoundand unreacted unsaturated perhalocarbon; and separating said phases.

13. A process for the allylic replacement of an unsaturatedperhalocarbon which comprises: reacting a perhalofiuoroallyl halidehaving at least 3 carbon atoms per molecule and an allylic halogen atomselected from the group'consisting of chlorine, bromine and iodine witha metal salt which is capable of releasing a negative ion in solutiondifferent from said allylic halogen atom and selected from the groupconsisting of metal alcoholates, iodides, cyanides and nitrates in awater-soluble solvent, whereby said allylic halogen atom is replacedwith the negative ion of the metal salt to produce a reaction masscomprising a substituted per-halofluoroallyl compound containing thenegative ion of said metal salt, solvent, a metallic allylic halogensalt precipitate and unreacted unsaturated perhalocarbon; re-

solution of sodium bisulfite having a concentration of at least 20% toform addition products with solvent present; and recovering saidsubstituted perhalofiuoroallyl compound from the addition products thusformed.

14. A process for the allylic replacement of an unsaturatedperhalocarbon which comprises: reacting a perhalofiuoroallyl halidehaving at least 3 carbon atoms per molecule and an allylic halogen atomselected from the group consisting of chlorine, bromine and iodine witha metal salt.- which is capable of releasing a negative ion in solutiondifierent from said allylic halogen atom and selected from the groupconsisting of metal alcoholates, iodides, cyanides and nitrates in awater-soluble solvent at a temperature between about 5 C. and about 100C., whereby said allylic halogen atom is replaced with the negative ionof the metal salt to produce a reaction mass comprising a substitutedperhalofiuoroallyl compound containing the negative ion of said metalsalt, solvent, a metallic allylic halogen salt precipitate and unreactedunsaturated perhalocarbon; recovering said precipitate from saidreaction mass; water-washing the remaining mixture, comprising saidsubstituted perhalofiuoroallyl compound and solvent to dissolve saidsolvent and form an aqueous phase comprising said solvent and an organicphase comprising said substituted perhalofluoroallyl compound andunreacted unsaturated perhalocarbon; separating said phases; contactingsaid organic phase with an aqueous solution of sodium bisulfite having aconcentration of at least 20% to form addition products with solventpresent; and recovering said substituted perhalofiuoroallyl compoundfrom the addition products thus formed.

15. A process for the allylic replacement of cFz CFCFzCl whichcomprises: reacting the aforesaid perhalocarbon with sodium methylate ina water-soluble solvent whereby CFFCFCF2OCH3 is produced.

16. A process for the allylic replacement oi CFFCFCFZC]. whichcomprises: reacting the aforesaid perhalocarbon with sodium iodide in aWater-soluble solvent whereby CFz=CFCF2I is produced.

17. A process for the allylic replacement of CF2=CFCF2C1 whichcomprises: reacting the aforesaid perhalocarbon with sodium cyanide in awatersoluble solvent whereby CFZZCFCF'ZCN is produced.

18. A substituted perhalofluoroallyl compound containing a negative ionof a metal salt selected from the group consisting of metal alcoholates,iodides, cyanides and nitrates, said negative ion being attached to anallyl carbon atom.

19. A substituted perchlorofiuoroallyl compound containing a negativeion of a metal salt selected from the group consisting of metalalcoholates, iodides, cyanides and nitrates, said negative ion beingattached to an allyl carbon atom.

20. 3-methoxyperfiuoropropene-1.

21. 3-iodoperfluoropropene-1.

22. B-cyanoperfluoropropene-l.

WILLIAM T. MILLER.

References Cited in the file of this patent UNITED STATES PATENTS NumberName Date 2,097,155 Groll et a1. Oct. 26, 1937 2,407,292 Salzberg Sept.10, 1946 2,409,274 Hanfold et al. Oct. 15, 1946 2,439,505 Chaney Apr.13, 1948 FOREIGN PATENTS Number Country Date 523,449 Great Britain July15, 1940 525,136 Great Britain Aug. 22, 1940 OTHER REFERENCES Fritsch,Beilstein (Handbuch, 4th Ed), vol. I, page 200 (1918).

Lespieau, Beilstein (I-Iandbuch, 4th Ed), vol. II, page 408 (1921).

Boeseken et al., Beilstein (Handbuch, 4th Ed.) 2nd Supp, vol. II, page137 (1929).

Adams et al., Organic Reactions, vol. II, pages 50-61, 84 (1944).

1. A PROCESS FOR THE ALLYLIC REPLACEMENT OF AN UNSATURATED PERHALOCARBON WHICH COMPRISES: REACTING A PERHALOFLUOROALLYL HALIDE HAVING AT LEAST 3 CARBON ATOMS PER MOLECULE AND AN ALLYLIC HALOGEN ATOM SELCECTED FROM THE GROUP CONSISTING OF CHLORINE BROMINE AND IODINE WITH A METAL SALT WHICH IS CAPABLE OF RELEASING A NEGATIVE ION IN SOLUTION DIFFERENT FROM SAID ALLYLIC HALOGEN ATOM AND SELECTED FROM THE GROUP CONSISTING OF METAL ALCOHOLATES, IODIES, CYANIDES AND NITRATES IN A SOLVENT SELECTED FROM THE GROUP CONSISTING OF WATER AND A WATER-SOLUBLE COMPOUND, WHEREBY SAID ALLYLIC HALOGEN ATOM IS REPLACED WITH THE NEGATIVE ION OF THE METAL SALT TO PRODUCE A REACTION MASS COMPRISING A SUBSTITUTED PERHALOFLUOROALLYL COMPOUND CONTAINING THE NEGATIVE ION OF SAID METAL SALT; AND RECOVERING SAID PERHALOFLUOROALLYL COMPOUND FROM SAID REACTION MASS.
 22. 3-CYANOPERFLUOROPROPENE-1 